1. Field of the Invention
The present invention relates to a solvent composition useful for liquid delivery chemical vapor deposition of metal organic precursors including metal (beta-diketonato) precursors.
2. Description of the Related Art
In the liquid delivery method of carrying out chemical vapor deposition (CVD) processes, a solid precursor is dissolved in an appropriate solvent mixture or a liquid-phase precursor is vaporized and the resulting precursor vapor, typically mixed with a carrier gas (such as argon, heliun or nitrogen) is transported to the chemical vapor deposition reactor. In the reactor, the precursor vapor stream is contacted with a heated substrate to effect decomposition and deposition of a desired component or components from the solution and/or vapor phase on the substrate surface.
In such liquid delivery CVD process, a wide variety of solvents have been employed for dissolution or suspension of precursor species, with the liquid solution or suspension being vaporized by various techniques, including flash vaporization on a heated element onto which the liquid containing the precursor is discharged, to volatilize the solvent and precursor species.
In many instances, where a variety of precursors are employed to form a multi-component deposited film in the CVD process, it is desirable to utilize a single solvent medium for the respective precursor species, for ease of operation and simplicity of the process system, thereby avoiding any deleterious solvent-solvent interactions which may occur if different solvent media are utilized for different precursor species. Further, it is desirable that solvent compositions when used for multiple species not interact with the precursor or metal-containing molecules to form unstable chemical solutions, since such instability renders the overall composition unsuitable for liquid delivery.
In a specific field in which the present invention has applicability, ferroelectric ceramic materials based on bismuth oxide are promising materials for use in non-volatile memories. Promising candidates derive from the group of Aurivillius phase compounds having the general formula:
(Bi2O2)2+(Amxe2x88x921BmO3m+1)2xe2x88x92,
wherein A=Bi3+, L3+, L2+, Ca2+, Sr2+, Ba2+, Pb2+, Na+, B=Fe3+, Al3+, Sc3+, Y3+, L4+, Ti4+, Nb5+, Ta5+, W6+, Mo6+, with L=metal from the lanthanide series, such as Ce4+, La3+, Pr3+, Ho3+, Eu2+, Yb2+, etc. and m=1, 2, 3, 4, 5.
Among materials of the foregoing type, SrBi2Ta2O9 (SBT) and Bi4Ti3O12 find widespread interest for integration in ferroelectric random access memories (FeRAMs) and in smart cards.
In chemical vapor deposition processes for SBT, the use of precursors such as Sr(thd)2(tetraglyme), Ta(OiPr)4(thd) and triphenyl bismuth, dissolved in a solvent medium such as tetrahydrofuran:isopropanol:tetraglyme in a volumetric ratio of 8:2:1 produced the result that Bi2O3 deposition was difficult to control. Efforts to resolve such difficulties included replacement of the triphenyl bismuth precursor with mononuclear Bi(thd)3 with the latter precursor showing a reliable and reproducible Bi2O3 deposition rate. Unfortunately, however, in the vaporizer the Bi(thd)3 precursor caused the formation of black bismuth-rich residues, indicating premature decomposition was taking place during vaporization and transport. Such premature decomposition allowed only ten operational runs to be conducted with the Bi(thd)3 precursor until the vaporizer required maintenance to remove unwanted deposits.
Chemical considerations associated with the foregoing adverse decomposition indicated the solvent system was one source of the problem. It appeared that in the presence of isopropanol dinuclear Bi(thd)3 precursor was formed and at the elevated temperature conditions of the vaporizer (190xc2x0 C.) the precursor was reduced to Bi metal producing the black residue. Concurrently, it is expected that the IPA is oxidized during this decomposition (redox) reaction.
Accordingly, an improved solvent system is desired for such deposition process for the formation of SBT films. Such a solvent system faces a number of problems. The solubility of the precursors in the solvent medium must be sufficiently high to provide adequate precursor delivery rates in the vaporizer. Moreover, there should not be a precipitation of material over a period of time due to any slight oversaturation incurred during preparation of the source reagent compositions, or caused by a ligand exchange among the different precursor species.
It therefore is the object of the present invention to provide a novel solvent composition having broad utility for CVD precursors, such as those comprising metal organic compositions with xcex2-diketonate ligands.
Other objects and advantages of the present invention will be more fully apparent from the ensuing disclosure and appended claims.
The present invention relates in one aspect to a solvent composition for liquid delivery chemical vapor deposition of metal organic precursors.
One composition of the invention comprises a mixture of solvent species A, B and C in the proportion A:B:C, wherein A is from about 1 to about 10 parts by volume, B is from about 0 to about 6 parts by volume, and C is present from 1 up to about 4 parts by volume, wherein such parts by volume are based on the total volume of the mixture, and wherein A is a C6-C8 alkane, B is a C8-C12 alkane, A and B are different from one another, and C is a glyme-based solvent (glyme, diglyme, triglyme, tetraglyme, etc.), a polyamine, and/or other suitable Lewis base ligand.
As used hereinafter, a Lewis base ligand is defined as a molecule that can donate an electron pair.
In one specific and preferred aspect, the solvent composition may comprise (A) octane, (B) decane, and (C) an amine, a diamine or a polyamine, in approximately 5:4:1 proportion (of A:B:C) by volume.
In another specific and preferred aspect, the solvent composition may comprise (A) octane and (C) an amine, a diamine or a polyamine, in approximately 9:1 proportion (of A:C) by volume.
Concerning preferred amine, diamine and polyamine species for component C in the composition of the solvent composition, preferred amine species include trialkylamine, preferred diamines include tetraalkyl ethylene diamine, and preferred polyamine species include N,N,Nxe2x80x2,Nxe2x80x2-tetramethylethylenediamine, N,N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x3-pentamethyldiethylenetriamine, and N,N, Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3,Nxe2x80x2xe2x80x3-hexamethyltriethylenetetramine.
In another aspect, the present invention relates to a precursor composition for liquid delivery chemical vapor deposition, comprising at least one metal organic precursor component in a solvent composition comprising a mixture of solvent species A, B and C in the proportion A:B:C wherein A is from about 1 to about 10 parts by volume, B is from about 0 to about 6 parts by volume, and C is present from 1 up to about 4 parts by volume, wherein such parts by volume are based on the total volume of the mixture, and wherein A is a C6-C8 alkane, B is a C8-C12 alkane, A and B are different from one another, and C is a Lewis: base ligand selected from the group consisting of glyme-based solvents (glyme, diglyme, triglyme, tetraglyme, etc.) ethers, amines, diamines and polyamines aryls and aryl amines. The metal organic precursor in such composition may for example comprise one or more metal xcex2-diketonate(s) and/or adduct(s) thereof.
In another aspect, the present invention relates to a precursor composition for liquid delivery chemical vapor deposition, comprising a bismuth Lewis base adduct precursor having the formula Bi(xcex2-diketonate)3(L)m, dissolved in a solvent composition comprising one or more alkanes and a Lewis base ligand, wherein L is a Lewis base ligand and m is a value between xc2xd and 5 and the Lewis base ligand of the precursor component and the Lewis base ligand of the solvent composition are the same.
In another aspect, the present invention relates to a precursor composition for liquid delivery chemical vapor deposition, comprising the metal organic precursor components Sr(xcex2-diketonate)2(L)m, Ta(alkoxide)4(xcex2-diketonate) and Bi(xcex2-diketonate)3(L)m, dissolved in a solvent composition comprising one or more alkanes and a Lewis base ligand, wherein L is a Lewis base ligand and m is a value between xc2xd and 5 and the Lewis base ligand of the precursor component and the Lewis base ligand of the solvent composition are the same.
In a preferred aspect, the present invention relates to a precursor composition for liquid delivery chemical vapor deposition, comprising Sr(thd)2(pmdeta), Ta(OiPr)4(thd) and Bi(thd)3(pmdeta), in a solvent composition comprising (A) octane, (B) decane, and (C) pmdeta, in approximately 5:4:1 proportion (of A:B:C) by volume.
Another aspect of the invention relates to a liquid delivery MOCVD method of forming a metal-containing film on a substrate including the steps of vaporizing a precursor composition to form a precursor vapor, and contacting the precursor vapor with the substrate to deposit said metal-containing film, wherein the precursor composition includes a solvent medium comprising one or more alkanes, having dissolved therein one or more compatible metal organic compound(s) selected from the group consisting of (i) xcex2-diketonate compound(s) and/or adducts thereof (ii) compound(s) including alkoxide ligands, and (iii) compound(s) including alkyl and/or aryl groups.
A further aspect of the invention relates to a process for forming a bismuth containing film on a substrate, in applications such as the formation of ferroelectric microelectronic device structures, comprising a bismuth Lewis base adduct precursor having the formula Bi(xcex2-diketonate)3(L)m, dissolved in a solvent composition comprising one or more alkanes and a Lewis base ligand, wherein L is a Lewis base ligand and m is a value between xc2xd and 5 and the Lewis base ligand of the precursor component and the Lewis base ligand of the solvent composition are the same.
In a still further aspect, the invention relates to a process for forming a film of SrBi2Ta2O9 (SBT) on a substrate, in applications such as the formation of ferroelectric microelectronic device structures, comprising the precursors Sr(xcex2-diketonate)2(L)m, Ta(alkoxide)4(xcex2-diketonate) and Bi(xcex2-diketonate)3(L)m in a solvent composition comprising one or more alkanes and a Lewis base ligand, wherein L is a Lewis base ligand and m is a value between xc2xd and 5 and the Lewis base ligand of the precursor component and the Lewis base ligand of the solvent composition are the same.
In a preferred aspect, the invention relates to a process for forming a film of SrBi2Ta2O9 (SBT) on a substrate, in applications such as the formation of ferroelectric microelectronic device structures, comprising the precursors Sr(thd)2(pmdeta), Ta(OiPr)4(thd) and Bi(thd)3(pMdeta), in a solvent composition comprising (A) octane, (B) decane, and (C) pmdeta approximately 5:4:1 proportion (of A:B:C) by volume.
In another preferred aspect, the invention relates to a process for forming a film of SrBi2Ta2O9 (SBT) on a substrate, in applications such as the formation of ferroelectric microelectronic device structures, comprising the precursors Sr(thd)2(pmdeta), Ta(OiPr)4(thd) and Bi(thd)3(pmdeta), in a solvent composition comprising (A) octane, and (C) pmdeta, in approximately 9:1 proportion (of A:C) by volume.
In another aspect, the invention relates to a process for forming a film of SrBi2Ta2O9 (SBT) on a substrate, in applications such as the formation of ferroelectric microelectronic device structures, wherein the precursors Sr(thd)2(tetraglyme), Ta(OiPr)4(thd) and Bi(thd)3 are employed in a solvent medium comprising one or more alkanes.
A still further aspect of the invention relates to a precursor composition for MOCVD of a metal-containing film on a substrate, wherein the precursor composition includes a solvent medium comprising one or more alkanes and/or arenes, having dissolved therein one or more compatible metal organic compound(s). Such compound(s) may for example be xcex2-diketonate compounds or complexes and/or adducts thereof, compound(s) including alkoxide ligands, compound(s) including alkyl and/or aryl groups at their outer (molecular) surface, or compound(s) including other ligand coordination species (i.e., Lewis base ligands) and specific metal constituents.
In one embodiment, such compound(s) may be selected from the group consisting of Sr(thd)2(tetraglyme), Sr(thd)2(Polyamine), Ba(thd)2(tetraglyme), Ba(thd)2(Polyamine), Ta(OiPr)4(thd), Ti(OiPr)2(thd)2, Zr(OiPr)2(thd)2, Bi(thd)3, Bi(thd)3(polyamine), Pb(thd)2, Pb(thd)2(tmeda), Pb(thd)2(pmdeta), Pt(thd)2, Pt(hfac)2, (methylcyclopentadienyl)Pt(Me)3, (MeCN)2PtMe2, Pd(allyl)2, Pd(hfac)2, Me2Au(hfac), MeAu(PMe3), Cu(hfac)2, (COD)Cu(hfac), (DMCOD)Cu(hfac), (MHY)Cu(hfac), (Me3P)CuOtBu, Ta(OR)5, and Ti(OR)4, wherein R=C1-C8 alkyl (branched or straight chain).
Other aspects, features and embodiments of the invention will be more fully apparent from the ensuing disclosure and appended claims.